KR960007776B1 - Precious metal coating accessories of plating a corrosion resistant copper alloy on first stage - Google Patents

Precious metal coating accessories of plating a corrosion resistant copper alloy on first stage Download PDF

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Publication number
KR960007776B1
KR960007776B1 KR1019930027896A KR930027896A KR960007776B1 KR 960007776 B1 KR960007776 B1 KR 960007776B1 KR 1019930027896 A KR1019930027896 A KR 1019930027896A KR 930027896 A KR930027896 A KR 930027896A KR 960007776 B1 KR960007776 B1 KR 960007776B1
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South Korea
Prior art keywords
plating
nickel
precious metal
tin
palladium
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KR1019930027896A
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Korean (ko)
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KR950016612A (en
Inventor
정주영
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범한정기 주식회사
정순호
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Priority to KR1019930027896A priority Critical patent/KR960007776B1/en
Publication of KR950016612A publication Critical patent/KR950016612A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Abstract

This accessories provide a combination of good brilliant colored surface and corrosion resistance, and prevents metal allergy being caused by nickel. The accessories coated with white precious metal are produced by the processes of (a) the primary coating of copper-tin alloy(5) containing 30 to 60wt.% tin in the thickness of over 0.5 Pm, and (b) the final coating of nickel-free palladium(3) to 0.1 to 5 Pm, and/or (c) the coating of nickel-free gold(6) to 0.1 to 5 Pm on the palladium coating layer. Or the accessories are produced by the processes of (a) the primary coating of copper-tin alloy having the same conditions as mentioned above, and (c) the final coating of nickel-free gold to 0.1 to 5 Pm. This method is used for watch case(1), spectacles, and necklace etc.

Description

초벌도금에 내식동합금 도금을 한 귀금속 도금장신구Precious metal plated jewelry with corrosion resistant copper alloy plating

제1도 및 제2도는 이 발명의 시계케이스의 일부 단면도.1 and 2 are partial cross-sectional views of the watch case of the present invention.

제3도는 종래의 시계케이스의 일부 단면도.3 is a partial cross-sectional view of a conventional watch case.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

1 : 시계케이스 2 : 니켈도금1: watch case 2: nickel plated

3 : 팔라듐도금(니텔을 불포함) 5 : Cu/Sn 도금3: Palladium plating (not including Nitel) 5: Cu / Sn plating

6 : 금도금 7 : 팔라듐도금(니켈포함)6: gold plating 7: palladium plating (including nickel)

이 발명은 금속알레르기 유발이 잘 안되고 광택내식성이 있는 귀급속 도금으로 처리한 장신구에 관한 것이다.This invention relates to jewelry treated with rapid metal plating, which is hard to cause allergic to metal and has corrosion resistance.

종래의 공지된 귀금속 도금으로 된 장신구는 귀금속 도금층의 초벌도금으로서 내식성, 광택성이 우수한 특성을 지닌 니켈도금이 많이 사용되었다.The jewelry of the conventionally known precious metal plating has been used nickel plating having excellent properties of corrosion resistance and glossiness as the primary plating of the precious metal plating layer.

니켈은 금속알레르기를 일으키기 쉬운 금속이기도 하며, 마무리층의 팔라듐 금도금 등 소실되거나, 마무리 도금층의 핀홀등을 통해서 용출한 니켈에 의해 알레르기를 일으키는 일이 있어, 니켈도금 대신에 금속알레르기가 잘 일어나기 힘든 초벌도금의 개발이 요구되고 있다.Nickel is also a metal that tends to cause metal allergens.It may be lost in palladium gold plating of the finishing layer, or allergic to nickel eluted through pinholes of the finishing plating layer. Development of plating is required.

시계, 안경, 목걸이 등의 장신구에 귀금속 도금을 하는 경우, 그 소재로써 황동, 니켈 실버(洋白)등이 주로 이용되고 그 도금의 종류로는 초벌도금으로 니켈을 입히고 백색도금의 경우에는 마무리 도금으로 팔라듐, 팔라듐니켈합금도금, 팔라듐합금 도금에는 로듐프레쉬도금이, 금색도금에는 금, 금합금 도금이 이용되고 있다.In the case of precious metal plating on jewelry such as watches, glasses and necklaces, brass, nickel silver, etc. are mainly used as the material, and the plating type is nickel-plated with primary plating, and in the case of white plating, finish plating. Therefore, rhodium fresh plating is used for palladium, palladium nickel alloy plating, and palladium alloy plating, and gold and gold alloy plating are used for gold plating.

니켈을 초벌도금, 마무리 도금층으로부터 삭제해 버려 금속알레르기가 잘 일어나지 않는 귀금속도금 장신구를 얻기 위해서는 초벌니켈도금을 삭제하고 직접, 니켈을 포함히자 않는 귀금속 도금을 하는 방법이 채용되고 있으나 내식성을 종래의 처리품과 비교해 동등 이상으로 하기 위해서는 귀금속 도금으로 도금 두께를 초벌니켈 도금에 상당하는 두께를 더 증가시켜 도금처리해야 하기 때문에 도금값이 비싸져서 코스트가 높아지는 문제가 있었다.In order to obtain precious metal plating ornaments in which nickel is removed from the primary plating and finishing plating layers, and metal allergy is less likely to occur, the primary nickel plating is removed and the precious metal plating which does not contain nickel is adopted. In order to make it equal to or more than the product, the plating thickness must be increased by increasing the thickness corresponding to the primary nickel plating with precious metal plating, and thus there is a problem that the plating value becomes expensive and the cost increases.

이 발명은 위에서 설명한 종래기술의 결점을 해소하기 위한 것으로, 금속알레르기의 원인이 되는 니켈을 사용하지 않고, 더우기 마무리 귀금속 도금과의 상성(相性)이 우수하고 광택, 내식성이 양호한 초벌도금방식을 채용하여 도금코스트가 저렴한 장신구를 제공하기 위하여 많은 검토를 한 결과 달성된 것으로 초벌도금으로 주석 30%~60%를 함유한 동/주석 합금도금을 0.5μ 이상 입히고, 백색 마무리 도금으로서 니켈을 포함하지 않는 팔라듐도금을 0.1~5μ 입히고 또 필요하다면 니켈을 포함하지 않은 금도금을 0.1~5μ 입히고 금색 마무리 도금에는 니켈을 포함하지 않는 금도금을 0.1~5μ 입히는 것을 특징으로 한다.This invention solves the drawbacks of the prior art described above, and employs a pristine plating method that does not use nickel, which causes metal allergy, and has excellent phase compatibility with the finished precious metal plating, and has good gloss and corrosion resistance. As a result of many studies in order to provide inexpensive jewelry, the plating cost was achieved by coating 0.5μ or more of copper / tin alloy plating containing 30% to 60% tin as the primary plating, and not including nickel as the white finish plating. It is characterized by coating 0.1 ~ 5μ of palladium plating and 0.1 ~ 5μ of gold plating without nickel if necessary and 0.1 ~ 5μ of gold plating without nickel for gold finish plating.

여기서 말하는 주석 30%~60% 함유한 동/주석 합금도금은 청화동-주석산알카리염제, 청화동-피로인산주석계, 피로인산동-피로인산주석계 등의 각종 동-주석합금도금조(糟)에서 얻을 수 있다. 이 발명자는 이 도금을 여러차례 검토한 결과 마무리 도금과의 조합에 의해 초벌니켈 보다도 내식성, 외관 특성이 우수하다는 것을 발견하여 이 발명을 완성하게 된 것이다.The copper / tin alloy plating containing 30% to 60% of tin is used in various copper-tin alloy plating tanks such as cyanide copper-tin acid alkali salts, cyanide copper-pyrophosphate tin system, and pyrophosphate copper-pyrophosphate tin system. Can be obtained from As a result of examining this plating several times, the inventors found that corrosion resistance and appearance characteristics were superior to those of the primary nickel by the combination with finish plating, thereby completing the present invention.

아래에서 이 발명에 시계용 케이스를 한 예로 하여 설명한다.Hereinafter, the watch case is described as an example of the present invention.

제1도와 같이 황동재로 된 시계용 케이스(1)에 주석30%~60%를 함유한 동/주석 합금도금(5)을 다음 도금액(초벌도금액), 도금조건에서 두께 3μ로 도금하고, 또한 니켈을 포함하지 않는 백색 마무리 도금액(백색 마무리 도금액), 도금조건으로 (3)을 3μ를 입혔다.As shown in FIG. 1, the copper / tin alloy plating (5) containing 30% to 60% of tin is plated to a thickness of 3 μ under the following plating solution (plating solution) and plating conditions in the watch case 1 made of brass. (3) was coated with 3 mu in the white finish plating liquid (white finish plating liquid) containing no nickel and plating conditions.

(초벌도금액)(Priority amount)

시안화동 금속동으로서 12g/l12 g / l as copper cyanide

유리시안 유리시안으로서 50g/l50 g / l as free cyan

주석산나트륨 금속주석으로서 20g/l20 g / l as sodium stannate

시안화아연 금속아연으로서 1.0g/l1.0 g / l as zinc cyanide metal zinc

황산납 금속납으로서 0.05g/l0.05 g / l as lead metal sulfate

로쎌염 20g/lRoot Salt 20g / l

계면활성제 0.1m/l0.1m / l surfactant

암모니아 2g/lAmmonia 2g / l

PH 12PH 12

양극 탄소Anode carbon

액온도 60oCLiquid temperature 60 o C

전류밀도 2A/dm2 Current density 2A / dm 2

도금시간 4분Plating time 4 minutes

(백색 마무리 도금액)(White finish plating solution)

아질산팔라듐암몬 금속납으로서 15g/lPalladium nitrite, lead metal, 15 g / l

질산암모늄 100g/lAmmonium Nitrate 100g / l

아질산암모늄 10g/lAmmonium Nitrite 10g / l

광택제 10g/lPolish 10g / l

PH 7.2PH 7.2

계면활성제 0.1m/l0.1m / l surfactant

양극 팔라듐Anode palladium

액온도 50oCLiquid temperature 50 o C

전류밀도 1A/dm2 Current density 1 A / dm 2

도금시간 12분Plating time 12 minutes

이상와 같이 하여 얻어진 백색귀금속처리를 한 시계케이스와 초벌도금처리를 하지 않고 직접, 니켈을 포함하지 않는 위 마무리 도금액으로 6μ의 팔라듐도금을 입힌 것과 비교한 결과, 귀금속도금이 얇아도 외관 특성 내식성 모두 이 발명의 초벌도금을 한 것이 우수하다는 것이 확인되었다.Compared to the watch case with the white noble metal treatment obtained above and the palladium plating with 6μ palladium coated with the above finish plating solution without nickel, the appearance characteristic corrosion resistance It was confirmed that the primary plating of the invention was excellent.

제2도와 같이 황동재로 된 시계용 케이스(1)에 주석 ㅊ30%~60%를 함유한 동-주석 합금도금(5)을 하기 도금액(초벌도금액), 도금조건으로 두께 3μ으로 도금하고, 다시 니켈을 포함하지 않는 금색, 금합금, 마무리 도금액(금색 마무리 도금액), 도금조건에서 (6)을 2μ 입혔다.As shown in FIG. 2, a copper-tin alloy plating 5 containing tin 30% to 60% in a brass watch case 1 was plated with a thickness of 3 μ under the following plating solution (plating solution), and plating conditions. (2) was applied to the gold, gold alloy, finish plating solution (gold finish plating solution), and plating conditions without nickel.

(금색 마무리 도금액)(Gold finish plating solution)

아황산금나트륨 금속Au로서 5g/l5 g / l as gold sodium sulfite metal Au

아황산팔라듐암몬 금속Pd로서 2g/lPalladium sulfite ammonium metal Pd 2 g / l

아황산나트륨 30g/lSodium sulfite 30g / l

EDTA.2Na 10g/lEDTA.2Na 10g / l

EDTA Cu 금속Cu로서 10ppm10 ppm as EDTA Cu metal Cu

광택제 1g/lPolish 1g / l

PH 7.5PH 7.5

양극 Ti/PtAnode Ti / Pt

액온도 55oCLiquid temperature 55 o C

전류밀도 0.5A/dm2 Current density 0.5 A / dm 2

도금시간 12분Plating time 12 minutes

이상와 같이하여 얻어진 금색 귀금속처리를 한 시계케이스와 초벌도금처리를 하지 않고 직접 니켈을 포함하지 않는 위 마무리 도금액으로 5μ의 금합금 도금을 입힌 것과 비교한 결과 귀금속도금이 얇아도 외관특성, 내식성, 모두 이 발명의 초벌도금을 한 것이 우수하다는 것이 확인되었다.Compared to the gold case of the gold precious metal treatment obtained above and 5μ gold alloy plating with the above finish plating solution which does not contain nickel directly without the primary plating treatment, the appearance characteristics, corrosion resistance, all It was confirmed that the primary plating of the invention was excellent.

이상 설명한 바와같이 이 발명의 초벌도금으로서 주석 30%~60%를 함유한 동-주석 합금 도금을 0.5μ 이상 입히고, 마무리 도금으로서 금속알레르기의 원인인 니켈을 포함하지 않는 귀금속 도금을 0.1~5μ 입힌 것이 보다 더 귀금속 도금을 얇게 할 수 있어 코스트 절감이 가능하고 금속알레르기 유발이 어려운 귀금속 도금을 입힌 귀금속 도금의 장신구를 쉽게 얻을 수 있으며 금속알레르기에 민감한 사람도 취급할 수 있는 효과가 있다.As described above, 0.5 micron or more of copper-tin alloy plating containing 30% to 60% of tin was coated as a primary plating of the present invention, and 0.1-5 micron of a noble metal plating containing no nickel, which is a cause of metal allergy, as a finishing plating. It is possible to reduce the precious metal plating more thinly, so that it is possible to reduce the cost and to easily obtain jewelry plated with precious metal plating, which is difficult to cause metal allergy, and to treat even people who are sensitive to metal allergy.

또한 실시예에서 시계케이스에 대해 말하였으나 다른 장신구에도 적용이 가능한 것은 물론이며 소재에 대해서도 황동뿐만 아니라 다른 소재도 가능하다. 또 실시예에서 언급한 이외에도 적절히 조합시켜 사용할 수도 있다.In addition, in the embodiment, the watch case is described, but it is also applicable to other ornaments, and of course, other materials may be used as well as brass. Moreover, it can also be used combining suitably other than what was mentioned in the Example.

Claims (3)

초벌도금으로서 주석 30%~60%를 함유한 동-주석 합금도금을 0.5μ 이상 입히고, 마무리 도금으로서 니켈을 포함하지 않는 팔라듐 도금을 0.1~5μ 입힌 것을 특징으로 하는 백색 귀금속 도금장신구.A white precious metal plated ornament, characterized in that a copper-tin alloy plating containing 30% to 60% of tin is coated as a primary coating, and 0.5 to 5 μm of palladium plating containing no nickel is used as a finish plating. 팔라듐도금위에 니켈을 포함하지 않는 금도금을 0.1~5μ 입힌 것을 특징으로 하는 백색 귀금속 도금장신구.White precious metal plated jewelry characterized by a gold plating 0.1 to 5μ not containing nickel on the palladium plating. 초벌도금으로서 주석 30%~60%를 함유한 동-주석 합금도금을 0.5μ 이상 입히고, 마무리 도금으로서 니켈을 포함하지 않는 금도금을 0.1~5μ 입힌 것을 특징으로 하는 백색 귀금속 도금장신구.White noble metal plating ornaments characterized by coating 0.5 micron or more of copper-tin alloy plating containing 30% to 60% of tin as the primary plating, and 0.1-5 microns of gold plating containing no nickel as the finishing plating.
KR1019930027896A 1993-12-15 1993-12-15 Precious metal coating accessories of plating a corrosion resistant copper alloy on first stage KR960007776B1 (en)

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KR960007776B1 true KR960007776B1 (en) 1996-06-12

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